INFLUENCE OF MULTIPLE HYDROGEN-BONDING ON REACTIVITY - ION MOLECULE REACTIONS OF PROTON-BOUND 12-CROWN-4 ETHER AND ITS MIXED CLUSTERS WITH AMMONIA AND METHANOL/

Reactions of protonated 12-crown-4 ether (Cr4 . H+) and its ammonium ( Cr4 . AH(+)) and methoxonium (Cr4 . MH(+)) ion complexes with a series of base molecules were studied using a selected ion flow tube. Reacti on efficiencies are enhanced for base molecules capable of forming mul tiple hydrogen bonded structures. The association kinetics of Cr4 . H were compared with those of the protonated dimer of 1,2-dimethoxyetha ne ((G1H+). insertion of ammonia into Cr4 . H+ is 8.8 times more effic ient than its insertion into (G1H+. The preferred reaction channel of Cr4 . MH(+) reactions is switching, while Cr4 . AH(+) undergoes associ ation as well as switching reactions. The reactivity and reaction patt erns of Cr4 . H+ and Cr4 . MH(+) are comparable to those of alkyl-bloc ked protonated dimers and trimers studied previously, while Cr4 . AH() has a different reactivity due to its hydrogen-bonding capabilities.